Tuning the intermolecular proton bond in the H5O2+ `Zundel ion' scaffold

TY - JOUR

T1 - Tuning the intermolecular proton bond in the H5O2+ `Zundel ion' scaffold

AU - Olesen, S. G.

AU - Guasco, T. L.

AU - Roscioli, J. R.

AU - Johnson, M. A.

PY - 2011/6/14

Y1 - 2011/6/14

N2 - The Zundel ion, H2O·H+·H2O, provides a versatile scaffold with which to explore the quantum structure of the intermolecular proton bond (IPB). This information is encoded in the vibrational frequencies adopted by the shared proton, νsp, which are observed to follow a remarkably similar trend as the exterior OH groups are sequentially solvated or are replaced by methyl substituents. In effect, solvents H-bonding to exterior OH groups act to increase the proton affinity of the water to which they are bound in a roughly additive fashion. We discuss this behavior in the context of the extreme sensitivity of IPBs to their solvation environments.

AB - The Zundel ion, H2O·H+·H2O, provides a versatile scaffold with which to explore the quantum structure of the intermolecular proton bond (IPB). This information is encoded in the vibrational frequencies adopted by the shared proton, νsp, which are observed to follow a remarkably similar trend as the exterior OH groups are sequentially solvated or are replaced by methyl substituents. In effect, solvents H-bonding to exterior OH groups act to increase the proton affinity of the water to which they are bound in a roughly additive fashion. We discuss this behavior in the context of the extreme sensitivity of IPBs to their solvation environments.

U2 - 10.1016/j.cplett.2011.04.060

DO - 10.1016/j.cplett.2011.04.060

M3 - Journal article

SN - 0009-2614

VL - 509

SP - 89

EP - 95

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 4-6

ER -